Manufacture of alcohols



Patented Dec. 22,1925.

UNITED STATES PATENT OFFICE.

CARNIE B. CARTER AND ALBERT. E. COKE, OE PITTSBURGH, PENNSYLVANIA, AS- I SIG-N035 TO S. KARPEN & 3308., OF CHICAGO, ILLINOIS, A CORPORATION OF WEST VIRGINIA.

Ifo Drawin g.

To all whom it may concern:

Be it known that we, CARN'IE B. CARTER and ALBERT E. Goxn, citizens of the United States, residing at Pittsburgh, in the county of Allegheny and State of Pennsylvania, have invented a new and useful Improvement in the Manufacture of Alcohols, of which the following is a specification.

The present invention relates particularly to the manufacture of alcohols by the action of a mono-halogenated hydrocarbon on an alkali in comparatively dilute alcoholic solution, the alcohol being of the aliphatic series.

The primary object is to. render it possible to produce alcohols synthetically by a di rect process from mono-halogenated hydrocarbons of the aliphatic series. Certain of these hydrocarbons can be produced either directly or indirectly from natural gas. Thus, the improved process enables a source of supply to be drawn from in the production of alcohols which has not heretofore been commercially available for such purpose.

The mono-halogenated hydrocarbon may be obtained for example, by chlorinatin methane or natural gas. The chlorine use in the chlorination process may be obtained by the electrolysls of sodium chloride.

of producing alcohol, the following may be given:

Introduce a quantity of methyl chloride and an alkali in a dllute aqueous methyl alcoholic solution into a vessel. A reaction will occur, and this reaction may be expedited by the use of heat. ;The reaction is preferably effected in a closed vessel, or under conditions which will keep themethyl d chloride, ora suflicient percentage of it in the liquor to effect the desired reaction. The

' reactionwill occur at room temperatures (say heated to 100 about 25 0.). However, if the vessel be C. the reaction will be greatly expedited andwill be completed, assuming the use of 15 to 20 per cent alcohol, in about an hour.

reaction to the As an illustration of the improved process MANUFACTURE OF ALCOHOLS.

Application filed August as, 1922. Serial 1%. 584,843.

The de ee of dilution of the liquor with water in uences the reaction. The methyl chloride reacts in two different ways, and thereby produces two difl'erent products, namely, alcohol and ether. The reaction which produces alcohol is made preponderant, or made to predominate, by increasing the degree of dilution of the alcohol with Water. The two reactions which occur in the illustration given, are:

'( 1) CH Cl+NaOH=NaGl+CH OH (2) CH,,Cl+CH,OH+NaOH= CH,,OOH,+NaOl+-H O. These two reactions take place simultaneously when an alkali (sodium, potassium and lithium) or alkaline earth (calcium, barium, strontium) hydroxide is treated with methyl chloride, and it is not possible to effect either absolute exclusion of' the other. However, the relative amounts of methyl alcohol and dimethyl ether resulting from the reaction can be governed within very wide limits. Thus, it is possible to make the bulk of the methyl chloride react in accordance with equation (1), or, on the other hand, the bulk of the chloride may be made to reactin accordance with equation (2). The determining factor is the degree of alcoholic concentration; low alcoholic concentration is conducive to the reaction set forth in equation (1), while high alcoholic concentration is conducive to the reaction set forth in equation (2) This is illustrated by the following experimental results obtained by using calcium hyroxide as the alkali and methyl chloride as the halogenated aliphatic hydrocarbon in aqueous methyl alcoholic solutions of varying alcoholic contents. Column 1 of the table shows the alcoholic content of the solution; column 2, the percentage of alcohol produced from the methyl chloride in accordance with equation v(1); and column'3, the percentage of dimethyl ether produced an aqueous alcoholic solution of l Alcohollcconcentration.

from the methyl chloride in accordance with equation (2) Methyl chloride.

To alcohol.

ceased ww-qoer- Percent.

In practice it is desirable to keep the alcoholic content of the liquor at or somewhat above 5%. In this manner about 90%of the methyl chloride reacting may be saponified directly to methyl alcohol and theremainder to dimethyl ether. The dimethyl etherzmay'be converted, if desired, into alcohol in any suitable manner.

Methyl chloride reacts very rapidly with sodium hydroxide, for example, in a 50% 85 water (100 C.) is a very suitable tempera- 'ture at which to operate the process; and vWhere pressure is employed, this may be simply the counter pressure which is developed in a closed vessel which varies in accordance 40 with the temperature employed in carrying on the reaction. a

In commercial practice, it is to be borne in mind that economy of manufacture will require that too great a dilution of the alcohol be not practiced, as the cost of handlingand fractionally distilling large volumes of weak liquors in order to recover small volumes of alcohol will militate against economy of operation. For this reason, too weak a solu- 60 tion ofalcohol is to be avoided; and, on the other'hand, the dilution should be kept sufliciently high to insure a preponderance of the reaction which directly produces alcohol. Unless some other factor enters to influence the/ course to be followed, it is desirable to use an alcoholic concentration which does ,not exceed 20% and the most desirable percentage will be somewhere betwln 5 and 15 per cent of alcohol in the liquor. To quite an extent, this will be governed by the use which can be'made of the ether which is produced' as a' byproduct. Thus, should there be a large demand for ether at any time, or 'slioulda very 'economical method of convert: 05 ing the ether into alcohol be or become availit is desirable to employ an alkali in excess 8 able, the percentage of ether produced in I the process maybe allowed to m'crease to' a considerable extent without detriment, and

economy would result in the production of the alcohol produced by the directmethod herein set forth. There is another factor to 1 be borne in mind, however. The production of dimethyl ether consumes some of the alcohol in the liquor. Accordingly, if the formation of the dimethyl ether becomes too great, the net yield of alcohol is correspondmgly reduced.

It may be stated here that in accordance with a published method of converting ether to alcohol, the ether is subjected to the action of an acid catalyst, suchasdilute sulphuric acid, heat and pressure being employed to eflect the conversion. In practice,

of the amount required to react with the halogenated hydrocarbon employed. This excess may be 100% without detriment to the practice of the process.

The following proportions of materials maiy be stated as an example? n an-autoclave dissolve 150 pounds of sodium hydroxide in 100 gallons of 5- per cent aqueous methyl alcohol solution, .add 100 pounds of methyl chloride, and heat until the reaction is complete. At a tempera- .ture of C. the reaction will be completed in about one hour. The reactions which occur produce alcohol, ether and sodium chloride. The'separaton of'the materials may be effected in any esired manner, or in the manner hereinafter' indicated. The methyl chloride employed is preferably introduced into the mixture as aliquid, although it 'may' be employed in the form of gas. It is convenient to have a stor- .age tank of methyl chloride, a storage tank of soduim hydroxide in'solution, and a storage tank of aqueous methyl alcohol, although the sodium hydroxide may .be em-' ployed in solid form, if desired. The sources 1. of supply may be connected with a suitable vessel to serve as a saponifier. If one starts with a 5% alcohol content inthe saponifier, for example, the process may be carried on until the alcoholic content in the saponifier rises to say 10 or 15 per cent. In the reaction sodium chloride is'produced, and this may be withdrawn from the saponifier. The

liquor in the saponifier. may be withdrawn, after the alcoholicconcentration reaches the desired stage, to a storage tank and from there may be taken, as, desired, into "a fractionating still. From-the fractionating still the alcohol distilled ofi' passes to an alcohol storage tank and the ether distilled c5 passes an ether-storage tank. The fractionatinp'; still may be connected with the aqueous methyl-alcohol storage tank to replenish the source of supply as mayjbe necessary. The other storage tank may be com I nected with a hydrolyzer, which turn may be connected with a storage tank which receives the hydrolized liquor. From this last mentioned storage tank the hydrolized 1i nor may pass to a fractionating still whic communicates with the methyl alcohol storage tank and also with an aqueous acid stor-' age tank. The aqueous acid storage tankmany be connected, in turn, with the hydrolyzer tank. Fresh supplies of the monohalogenated hydrocarbon and of the alcohol may be introduced into the corresponding storage tanks as required. The method here stated provides for a continuous o eratlon of the process. By this process, al of the methyl chloride may be ultimately converted into the methyl alcohol.

It will be' readily understood that the character of the alcohol produced wlll depend upon the materials employed. Thus,

- the use of methyl chloride leads to the production of methyl alcohol; and the use of ethyl chloride leads to the productlonof ethyl alcohol; also, the use of propyl chloride leads to the reduction of propyl alcohol. It is desirab e, of course, to carry out the reaction in any selected case 1n the presence of a comparatively dilute solution of alcohol of the same character as that which is to be produced. Other alcohols may be produced in an analogous manner by using the appropriate mono-halogenated hydrocarbon.

It may be stated that the reaction when carried out with certain combinations of alkyl halides with certain aliphatic alcohols used as solvents may produce a variety of normal and mixed others as a by-pro not The temperature at which the reaction may be effected may .be any desired temperatune, but, as has been indicated, an elevated temperature is preferred, such as a temperature of in-the neighborhood of 100 C.

It is desirable to employ the alkyl halides and the alkali in substantially molecular proportions. Any suitable alkali ma be employed, that is, while the hydroxi e is preferably emplo ed, some other compound may be employe such as carbonatev or bicarbonate of an alkali metal.

Examples of monodialogenated hydrocarbons of the aliphatic series, or alkyl halides, which may be employed, are as follows:

Methyl chloride CH Cl).

Ethyl chloride H 61).

Propyl chloride (0 11,01

Isobutyl chloride (CJ-I l).

Iodides and brom1des of the same character, belongin to the mono-halogenated hydrocarbonso the aliphatic series, may be employed in the process.

Examples of alcohols of the aliphatic series which may be employed inthe process are as follows:

Methyl alcohol (CI-LOH).

Ethyl alcohol (0 H,,OH).

Normal prop 1 alcohol (CJLOH).

Isobutyl alco ol (G,H,,OH).

Examples of alkalies which may be .employed in the process are as follows:

Sodium hydroxide (qNaOH).

Potassium hydroxide (KOH).

Sodium carbonate (Na CO Sodium bicarbonate (NaHCO Potassium carbonate (K CO Potassium bicarbonate (KHCO Calcium hydroxide Ca(OH) 'As has been indicated, methyl chloride may be obtained directly from natural as or other gas,"'by a chlorinating process. fie same is true of some of the other chlorides, while other mono-halogenated hydrocarbons may be obtained indirectly from gas. Thus, natural gas, or other gas, may be the ultimate source of supply for obtaining an of the desired halogenated hydrocarbons of the aliphatic series for the purpose of producing alcohol in accordance with the present process.

The materials undergoing reaction ma be present in varying proportions, inasmuch as, under the conditions set forth, the will unite in proper roportions to form a cohol as the main pro net and ether as a by-prodpet. The pressure which arises during the reaction in a closed vessel, whether at ordinary room tem eratures, or at elevated temperatures, is su cient to maintain a sufficient amount of the halogenated hydrocarbon in solution to permit the reaction to proceed. At elevated temperature, the reaction is expedited, the pressure being cor 'respondingly increased. Application of pressure from an external source is unnecessary but maybe used, if desired. The pressure may vary, depending upon the materials employed, the product produced, and the temperature, from a few pounds to perhaps three or four hundred pounds per square inch. It is to be remarked that the chief function of. the alcohol in the carrying out of the process is that of placing the chlorinated roduct more readily in solution. On the ot er hand, the use of a large percentage of water and a small percenta OI alcohol favors the placing of the alkali in solution as such, rather than the formation of an alcoholate and it is to this feature that the preponderant production of alcohol is to be attributed. On the other hand, the

chlorinated hydrocarbon is soluble to a certain degree in water alone, hence, it is perfectly possible to begin the operation ofthe process in the presence of little or-no alcohol; and, as the operation proceeds, the desired degree of concentration of alcohol willbe acquired by the liquor. Thereafter, the degree of concentration of alcohol in the liquor may be re ated in accordance with the most economical procedure, alcohol being distilled off from time to time as to coho] which com rises causing a reaction bebest accord with economical operation. tween amono-ha o enated hydrocarbon and The foregoing. detailed description has an alkali dissolved 1n water and a small perbeen given for clearness of understandin r centage of an alcohol of the aliphatic'series, 15

B only and no necessary limitations shoulr such reaction being efiected'at a temperature be understood therefrom, but the appended .of approximately 100 C., under pressure, claims should be construed as broadly as and removing alcohol from time to time permissible in' View ofthe prior art. to maintain a concentrationof alcohol which I .What we regard as new, and desire to scis lower than 20%. lo cure by Letters Patent, isp CARNI'E B. CARTER.

The continuous process of producing al- ALBERT E. 

